CN103946210B - β-mercaptan carboxylic acid's manufacture method - Google Patents
β-mercaptan carboxylic acid's manufacture method Download PDFInfo
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- CN103946210B CN103946210B CN201280057346.4A CN201280057346A CN103946210B CN 103946210 B CN103946210 B CN 103946210B CN 201280057346 A CN201280057346 A CN 201280057346A CN 103946210 B CN103946210 B CN 103946210B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/04—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by addition of hydrogen sulfide or its salts to unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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Abstract
β-mercaptan carboxylic acid's that following general formula of the present invention (3) represents manufacture method comprises following operation: under normal pressure, (X represents Na, K to make hydrogen sulfide, formula XOH. ) alkali metal hydroxide representing and the unsaturated carboxylic acid reaction of following general formula (1) expression, obtain the operation of the reactant liquor of the compound that comprises following general formula (2) expression, with the operation with the reactant liquor of gained in the aforementioned operation of acid neutralization, wherein, the amount of described alkali metal hydroxide is more than the total molal quantity of described unsaturated carboxylic acid and described hydrogen sulfide.
Description
Technical field
The present invention relates to use the β-mercaptan carboxylic acid's of unsaturated carboxylic acid manufacture method.
Background technology
β-mercaptan carboxylic acid is as the raw material using agricultural chemicals, medicine as the organic synthesis product of representative and is the useful compound of raw material as crosslinking agent, the plastic lens monomer etc. of stabilizing agent, epoxy resin or the acrylate polymer of vinyl chloride.
As β-mercaptan carboxylic acid's manufacture method, can enumerate following such method.
In patent documentation 1, record acrylic acid and thiosulfate are reacted in aqueous medium, generated Bang Te (Bunte) salt as β-mercaptopropionic acid precursor, then under sour existence, made the method for this bunte salts hydrolysis.
In patent documentation 2, record under the existence of alkali metal hydroxide (alkalihydroxide), in the aqueous solution of alkali metal hydrosulfide (alkalihydrosulfide), add alkali metal salts of acrylic acids (acrylicacidalkalisalt) aqueous solution to make its reaction, with acid neutralization, and then use zinc reduce the method for processing.
In patent documentation 3, record unsaturated carboxylic acid is reacted with sulfohydrate, the reaction medium acidifying of gained is obtained in mercaptan carboxylic acid's method, supply with by the hydrogen sulfide in unsaturated carboxylic acid and beyond the hydrogen sulfide of supplying with, and at least 8 methods of reacting of depressing that add of clinging to (bar). In addition, recorded sulfohydrate by H2S obtains with reacting of NaOH etc.
Patent documentation 4 has been recorded under the existence of alkali compounds, and beta-unsaturated carboxylic acid is reacted in the aqueous solution with hydrogen sulfide, manufactures β-mercaptan carboxylic acid's method, wherein, carries out above-mentioned reaction under the pressure condition of 3.5～20.0MPaG.
Patent documentation 5 has been recorded to adding in the alkali metal hydrosulfide aqueous solution unsaturated nitrile to make its reaction, neutralizes, is hydrolyzed and while manufacturing mercaptan carboxylic acid, use sulphur.
Patent documentation 1: No. 59-29633, Japanese kokai publication sho
Patent documentation 2: No. 2001-187778, TOHKEMY
Patent documentation 3: No. 2000-501723, Japanese Unexamined Patent Application Publication
Patent documentation 4: No. 2010/095745 brochure of International Publication
Patent documentation 5: No. 2-121962, Japanese kokai publication hei
Summary of the invention
In the technology of recording at above-mentioned patent documentation, there is following such problem.
In the reaction of patent documentation 2, need to use alkali metal hydrosulfide as raw material. But owing to having generated the more two sulfo-dicarboxylic acids as accessory substance, therefore reaction yield declines sometimes. In addition, although can obtain β-mercaptan carboxylic acid by reducing two sulfo-dicarboxylic acids, because the use amount of reducing agent increases, therefore manufacturing cost increases, and also has the problem that discarded object increases after reaction. It should be noted that, as above, for the explanation of patent documentation 5, the method characteristic of the document is not use hydrogen sulfide.
In patent documentation 3 or 4, owing to reacting adding to depress, therefore need to maintain pressurized state, manufacturing processes etc. are numerous and diverse. In addition, need to be provided in addition manufacturing equipment, the pressure-resistant equipment of pressurization, the burden of manufacturing cost increases. It should be noted that, in the comparative example 1 of patent documentation 4, recorded the example reacting under normal pressure, but reaction yield still has room for improvement.
The invention solves the problems referred to above, can be described below.
[1] β-mercaptan carboxylic acid's that following general formula (3) represents manufacture method, is characterized in that, comprises following operation:
Under normal pressure, (X represents Na, K to make hydrogen sulfide, formula XOH. ) the unsaturated carboxylic acid reaction that represents of the alkali metal hydroxide that represents and following general formula (1), obtain comprising the operation of the reactant liquor of the compound that following general formula (2) represents, and
Neutralize the operation of the reactant liquor of gained in aforementioned operation with acid,
Wherein, the amount of described alkali metal hydroxide is more than the total molal quantity of described unsaturated carboxylic acid and described hydrogen sulfide.
(in formula (1), R1、R2The alkyl that represents respectively hydrogen or C1～C4, can be the same or different. )
(in formula (2), R1、R2Identical with the implication in formula (1), the implication in the alkali metal hydroxide that X represents with formula XOH is identical. )
(in formula (3), R1、R2Identical with the implication in formula (1). )
[2] manufacture method of the β-mercaptan carboxylic acid described in above-mentioned [1], is characterized in that, the described operation that obtains reactant liquor is carried out under sulphur exists.
[3] manufacture method of the β-mercaptan carboxylic acid described in above-mentioned [1] or [2], is characterized in that, comprises the operation of the two sulfo-dicarboxylic acids that generated by β-mercaptan carboxylic acid with metallic reducing by the described operation of sour neutralization reaction liquid.
Under so-called normal pressure, be the scope of 0.09～0.13MPa left and right, comprise the micro-pressurized state producing while being blown into hydrogen sulfide.
According to the present invention, can under normal pressure, obtain mercaptan carboxylic acid with high yield. In addition,, by using hydrogen sulfide as raw material, the generation of the two sulfo-dicarboxylic acids as accessory substance that occurred while having suppressed neutralization reaction liquid, can be provided in industrial also easy method.
Detailed description of the invention
Below, the present invention is described.
β-mercaptan carboxylic acid's of the present invention manufacture method has following operation a and operation b.
Each operation is described successively.
[operation a]
Under normal pressure, (X represents Na, K to make hydrogen sulfide, formula XOH. ) the unsaturated carboxylic acid reaction that represents of the alkali metal hydroxide that represents and following general formula (1), obtain comprising the reactant liquor of the compound that following general formula (2) represents.
In formula (1), R1、R2The alkyl that represents respectively hydrogen or C1～C4, can be the same or different.
In formula (2), R1、R2Identical with the implication in formula (1), the implication in the alkali metal hydroxide that X represents with formula XOH is identical.
In operation a, the amount of alkali metal hydroxide is more than general formula (1) unsaturated carboxylic acid and the total molal quantity of hydrogen sulfide that represent. Thus, even under normal pressure, also can obtain mercaptan carboxylic acid with high reaction yield.
It should be noted that, with respect to the total molal quantity of unsaturated carboxylic acid and hydrogen sulfide, the amount of alkali metal hydroxide is preferably more than 1 times, more preferably more than 1.5 times. If the sour amount of neutralization reaction liquid increases the viewpoint consideration that increase exerts an influence to cost from reaction finishes, higher limit is below 5 times, is preferably below 4 times, more preferably below 2.5 times. These higher limits and lower limit can be combined.
In the present invention, operation a can be undertaken by following method.
(1) in alkali metal hydroxide aqueous solution, add the unsaturated carboxylic acid that general formula (1) represents, form salt. Then be blown into hydrogen sulfide, make itself and unsaturated carboxylic acid reactant salt.
(2) in alkali metal hydroxide aqueous solution, be blown into hydrogen sulfide, then add the unsaturated carboxylic acid that general formula (1) represents, make its reaction.
It should be noted that, in method (1) and (2), be illustrated by the example that adds unsaturated carboxylic acid, but also can use the previously prepared unsaturated carboxylic acid alkali metal salt of alkali metal hydroxide (alkalisaltofunsaturatedcarboxylicacid) to use. At this moment, operation a can be undertaken by following method (3).
(3) in alkali metal hydroxide aqueous solution, be blown into hydrogen sulfide, then add unsaturated carboxylic acid aqueous solution of alkali metal salt and react, described unsaturated carboxylic acid aqueous solution of alkali metal salt is prepared in addition by add unsaturated carboxylic acid in alkali metal hydroxide aqueous solution.
It should be noted that, method (3) in the situation that, the amount that the amount of alkali metal hydroxide comprises the alkali metal hydroxide for generating in advance unsaturated carboxylic acid alkali metal salt.
In operation a, as the unsaturated carboxylic acid of general formula (1), preferably R1、R2Represent independently of one another hydrogen or methyl, specifically can enumerate acrylic acid, methacrylic acid, butenoic acid etc. In the time of the β-mercaptopropionic acid of manufacturing for plastic lens monomer etc., can use acrylic acid.
By formula XOH, (X represents Na, K to alkali metal hydroxide. ) represent, X is preferably sodium. Alkali metal hydroxide can, as recorded in said method, use with aqueous solution form, but also can be dissolved in the mixed solvent of water/alcohol, can also add in addition alcohol. Compared with previous methods with an organic solvent, do not need solvent recovery operation etc., aspect boosting productivity, be favourable.
As hydrogen sulfide, can enumerate from the hydrogen sulfide of petroleum refining, by sulphur hydrogenation and synthetic hydrogen sulfide etc. In operation a, when supplying with hydrogen sulfide in alkali metal hydroxide aqueous solution, can use with hydrogen sulfide gas form, but consider from the viewpoint of excellent storage stability, conventionally process with liquefaction hydrogen sulfide form.
With respect to unsaturated carboxylic acid, more than the amount of the hydrogen sulfide of interpolation is preferably 1.0 equivalents, more preferably more than 1.5 equivalents. Higher limit is below 9.0 equivalents, is preferably below 5.0 equivalents, more preferably below 3.0 equivalents. These higher limits and lower limit can be combined.
Can the temperature of alkali metal hydroxide aqueous solution be remained on to 0～50 DEG C on one side, in this aqueous solution, supply with hydrogen sulfide gas on one side. Thus, the solubility of hydrogen sulfide gas improves,
Be swift in response and carry out. Supply with after hydrogen sulfide gas, conventionally 20～150 DEG C, preferably 50～140 DEG C, more preferably in the temperature range of 80～130 DEG C, react. Said temperature scope if, considers it is preferred from the viewpoint of reaction speed, minimizing accessory substance (two sulfo-dicarboxylic acids, sulfo-dicarboxylic acids) output. Reaction time can suitably be selected according to reaction temperature, is generally 0.5～20 hour, is preferably 1～15 hour, and more preferably 2～10 hours, more preferably 3～10 hours.
In addition, in operation a, in order to promote reaction, can under existing, sulphur react. Thus, can within the shorter time, complete mercaptan carboxylic acid's reaction.
Consider from the viewpoint of above-mentioned effect, the addition of sulphur is 0.01～10 % by mole with respect to unsaturated carboxylic acid, is preferably 0.1～5 % by mole, more preferably 0.1～3 mole. Adding method is not particularly limited, but in the time adding unsaturated carboxylic acid or unsaturated carboxylic acid alkali metal salt, is preferably present in the aqueous solution.
By operation a, can obtain the reactant liquor of the compound that contains general formula (2) expression. Except this compound, in reactant liquor, also contain sulfo-dicarboxylic acids etc.
[operation b]
With the reactant liquor of gained in acid and in operation a, the compound being represented by general formula (2) obtains β-mercaptan carboxylic acid that following general formula (3) represents.
In formula (3), R1And R2Identical with the implication in formula (1).
As acid, can use the inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, the low-grade carboxylic acids such as formic acid, acetic acid etc.
Acid can be used to be acid amount in reaction system, conventionally, with respect to the alkali metal hydroxide using in reaction, is suitably for the scope of 0.8～1.2 equivalent. In the time adding, preferably use pH meter to confirm the pH of reactant liquor on one side, implement on one side to add, pH is set as 1～3.
By operation b, can obtain containing β-mercaptan carboxylic acid that general formula (3) represents and the reactant liquor of sulfo-dicarboxylic acids. Except these compounds, in reactant liquor, also contain two sulfo-dicarboxylic acids that generated by β-mercaptan carboxylic acid etc.
[reduction operation]
In the present invention, consider from the viewpoint that improves β-mercaptan carboxylic acid yield, can comprise the operation of the two sulfo-dicarboxylic acids that generate with metallic reducing. It should be noted that, this reduction operation can be carried out after operation b (in and operation), or carries out with operation b simultaneously.
In reduction operation, directly do not obtain target beta-mercaptan carboxylic acid by the reactant mixture after neutralization, the liquid after finishing to reaction or by and in the reactant liquor of gained, add reducing agent, under acid condition, carry out reduction reaction. Thus, the two sulfo-dicarboxylic acids as accessory substance can be converted into β-mercaptan carboxylic acid, can realize the raising of yield.
As the metal of reducing agent, can use zinc, iron, tin etc. Wherein, consider from economy and the viewpoint that alleviates carrying capacity of environment, preferably use iron. It should be noted that, these reducing agents can use separately respectively a kind, or also two or more can be used in combination. Consider from the viewpoint that improves yield and economy, with respect to 1 mole of two sulfo-dicarboxylic acids that generate as accessory substance, the use amount of reducing agent is preferably 1.0～5 moles, more preferably 1.2～3 moles.
Manufacture method of the present invention is compared with adding the method for NaSH, and the output of two sulfo-dicarboxylic acids is few, can improve β-mercaptan carboxylic acid's reaction yield. In addition,, because the output of two sulfo-dicarboxylic acids is few, therefore can reduce the amount from the discarded object of the metal for reducing.
In water layer due to gained after neutralization, be dissolved with β-mercaptan carboxylic acid, therefore utilize organic solvent to extract from water layer. As organic solvent, can use ethyl acetate, butyl acetate, chloroform, carrene, ether, isopropyl ether, MEK, isobutyl ketone etc., preferably use ethyl acetate, butyl acetate etc.
After extraction, by the concentrated organic solvent that heats up in a steamer under decompression or normal pressure, then distill and refine, can obtain thus target mercaptan carboxylic acid. It should be noted that the inorganic salt solution such as saltcake or salt that after extraction, the aqueous solution of gained is high concentration for example, can be used as the highly purified saltcake aqueous solution and uses. In addition, if from the saltcake solution of high concentration crystallization, the crystallization of separating out can be used as the very high saltcake of purity and uses. And then, owing to also containing hardly organic matter, nitrogen compound in waste liquid, therefore environment not being affected, the public hazards of carrying out are processed also very easy, economical.
In the time that distillation is refining, be not particularly limited for the distilling apparatus distilling, can use the known distilling apparatus such as batch distillation device, continous way distilling apparatus, tower distilling apparatus. In the time of industrial a large amount of distillation, from making stay in grade, boost productivity etc., viewpoint is considered, preferably uses the continuous rectification apparatus that comprises heater, rectifying column and condenser.
In addition, after distillation, in residue, contain the sulfo-dicarboxylic acids as accessory substance. These bottoms can also be back to again to operation a (recirculation operation). Contained sulfo-dicarboxylic acids in bottoms, can be as β-mercaptan carboxylic acid's raw material. At this moment, consider from the viewpoints such as fluidity of moving of bottoms, in order to give mobility, heat, or use solvent dilution bottoms, these bottoms can be back to reaction process for reaction. In addition, in distillation process, also can not distillate whole β-mercaptan carboxylic acids, and finish distillation with residual 5～50%, preferably 10～30% state in bottoms, be back to reaction process for reaction with the form of β-mercaptan carboxylic acid solution of sulfo-dicarboxylic acids.
By repeating described operation, can improve β-mercaptan carboxylic acid's ultimate yield.
Above, describe the present invention, but not damaging in the scope of effect of the present invention, also can adopt other formations.
Embodiment
Below, wait and be described more specifically the present invention by embodiment, but scope of the present invention is not limited to these embodiment etc.
(embodiment 1)
Preparation has agitating device, thermometer, cooling tube, dropping funel, is blown into 5 mouthfuls of flasks of pipe, packs into after 36.3g (0.88mol) 97% NaOH and 43.3g water, stirs until become even. In oil bath, heat flask, interior temperature is remained on to 45～50 DEG C on one side, dripped 14.4g (0.20mol) acrylic acid on one side by dropping funel through 0.5 hour.
After dropping finishes, at the same temperature, through 88 points of clockwise reactant liquors, be blown into 12.6g (0.37mol) hydrogen sulfide gas via flowmeter from liquefaction hydrogen sulfide bottle (Sumitomo Seika Co., Ltd's system). Be blown into after end, be warming up to 100 DEG C, at this temperature, carry out reaction in 8 hours. It should be noted that, after starting 5 hours, reaction use HPLC to carry out quantitative analysis to reactant liquor, result is, generated 76.1mol% β-mercaptopropionic acid sodium salt, 23.1mol% thio-2 acid sodium salt and 0.3mol% dithio dipropyl acid sodium-salt as accessory substance.
Reaction finishes rear reactant liquor to be carried out to quantitative analysis, result is, has generated 86mol% β-mercaptopropionic acid sodium salt, 13mol% thio-2 acid sodium salt and 0.4mol% dithio dipropyl acid sodium-salt as accessory substance.
On one side, to bubbling nitrogen in reaction system, dripped 129.5g (0.462mol) 35% aqueous sulfuric acid, neutralization reaction liquid on one side through 2.5 hours. At this moment the hydrogen sulfide producing is expelled to outside system by cooling tube top. In addition, the reaction mass after neutralization consists of β-mercaptopropionic acid 86mol%, thio-2 acid 13mol%, dithiodipropionic acid 0.3mol% as accessory substance.
After degassed end, pack 18.0g butyl acetate into, carry out extracting operation. In the water layer of separatory gained, further pack 18.0g butyl acetate into, implement same extracting operation, implement altogether 3 times.
After the butyl acetate layer of 3 extraction gained is merged together, use evaporimeter under reduced pressure to heat up in a steamer butyl acetate. The concentrate of gained is encased in the still of the distilling apparatus with single tube, under the decompression of 1.2KPa, distills. In the time that rising to 150 DEG C, still temperature finishes distillation. In this still, the proterties of residue is, even if also have mobility at 100 DEG C. Obtain the β-mercaptopropionic acid that 17.5g (0.165mol) is 99.9% as the purity of main distillate fraction. Be 82.5% with respect to acrylic acid yield.
(embodiment 2)
Preparation has agitating device, thermometer, cooling tube, dropping funel, is blown into 5 mouthfuls of flasks of pipe, packs into after 36.3g (0.88mol) 97% NaOH and 43.3g water, stirs until become even. In oil bath, heat flask, interior temperature is remained on to 45～50 DEG C on one side, dripped 14.4g (0.20mol) acrylic acid on one side by dropping funel through 0.5 hour.
After dropping finishes, at the same temperature, through 88 points of clockwise reactant liquors, be blown into 12.6g (0.37mol) hydrogen sulfide gas via flowmeter from liquefaction hydrogen sulfide bottle (Sumitomo Seika Co., Ltd's system). Be blown into after end, be warming up to 100 DEG C, at this temperature, carry out reaction in 8 hours.
Reaction finishes rear use HPLC reactant liquor is carried out to quantitative analysis, result is, has generated 86.1mol% β-mercaptopropionic acid sodium salt, 12.9mol% thio-2 acid sodium salt and 0.4mol% dithio dipropyl acid sodium-salt as accessory substance.
In reaction system, pack into after 0.04g (0.0007mol) Fe powder, on one side, to bubbling nitrogen in reaction system, dripped 129.5g (0.462mol) 35% aqueous sulfuric acid, reduction neutralization reaction liquid on one side through 2.5 hours. At this moment the hydrogen sulfide producing is expelled to outside system by cooling tube top. Reaction mass after neutralization consists of β-mercaptopropionic acid 86.5mol%, does not detect as thio-2 acid 12.9mol%, the dithiodipropionic acid of accessory substance.
(embodiment 3)
Preparation has agitating device, thermometer, cooling tube, dropping funel, is blown into 5 mouthfuls of flasks of pipe, pack into after 36.3g (0.88mol) 97% NaOH, 43.3g water and 0.072g (0.0022mol) sulphur, stir until become even.
In oil bath, heat flask, interior temperature is remained on to 45～50 DEG C on one side, dripped 14.4g (0.20mol) acrylic acid on one side by dropping funel through approximately 0.5 hour.
After dropping finishes, at the same temperature, through 88 points of clockwise reactant liquors, be blown into 12.6g (0.37mol) hydrogen sulfide gas via flowmeter from liquefaction hydrogen sulfide bottle (Sumitomo Seika Co., Ltd's system). Be blown into after end, be warming up to 100 DEG C, start reaction. Implement the response analysis program analysis (RAPANALYSIS) of reaction mass on one side, react on one side, the yield of result β-mercaptopropionic acid sodium salt after reaction starts 2 hours is 84.0mol%, generates 14.9mol% thio-2 acid sodium salt, 0.5mol% dithio dipropyl acid sodium-salt as accessory substance.
Reaction starts to finish after 5 hours, and the yield of result β-mercaptopropionic acid sodium salt is 87.4mol%, generates 11.8mol% thio-2 acid sodium salt, 0.8mol% dithio dipropyl acid sodium-salt as accessory substance.
(embodiment 4)
Preparation has agitating device, thermometer, cooling tube, dropping funel, is blown into 5 mouthfuls of flasks of pipe, pack into after 47.0g (1.14mol) 97% NaOH, 54.5g water and 0.072g (0.0022mol) sulphur, stir until become even.
In oil bath, heat flask, interior temperature is remained on to 45～50 DEG C on one side, dripped 14.4g (0.20mol) acrylic acid on one side by dropping funel through 0.5 hour.
After dropping finishes, at the same temperature, through 90 points of clockwise reactant liquors, be blown into 17.7g (0.52mol) hydrogen sulfide gas via flowmeter from liquefaction hydrogen sulfide bottle (Sumitomo Seika Co., Ltd's system). Be blown into after end, be warming up to 100 DEG C, at this temperature, carry out reaction in 8 hours.
Reaction finishes rear use HPLC reactant liquor is carried out to quantitative analysis, result is, has generated 94.8mol% β-mercaptopropionic acid sodium salt, 4.6mol% thio-2 acid sodium salt and 0.2mol%2 thio-2 acid sodium salt as accessory substance.
(embodiment 5)
Similarly operate with embodiment 1, obtain the β-mercaptopropionic acid that 17.5g (0.165mol) is 99.9% as the purity of main distillate fraction, 2.8g is as (β-mercaptopropionic acid 15.7wt% (0.004mol), thio-2 acid 81.5wt% (0.012mol), dithiodipropionic acid 2.3wt% (0.0003mol)) (reaction 1) of pressure bottoms (bottoms (A)).
Preparation has agitating device, thermometer, cooling tube, dropping funel, is blown into 5 mouthfuls of flasks of pipe, packs into after 36.3g (0.88mol) 97% NaOH and 43.3g water, stirs until become even. To slowly add in this sodium hydrate aqueous solution 2.8g insulation to 90～95 DEG C, there are the bottoms (A) (ratio of components: β-mercaptopropionic acid 15.7wt%, thio-2 acid 81.5wt%, dithiodipropionic acid 2.3wt%) of the state of mobility. Interior temperature is remained on to 45～50 DEG C on one side, dripped 12.24g (0.17mol) acrylic acid on one side by dropping funel through 0.5 hour.
After dropping finishes, at the same temperature, through 90 points of clockwise reactant liquors, be blown into 12.6g (0.37mol) hydrogen sulfide gas via flowmeter from liquefaction hydrogen sulfide bottle (Sumitomo Seika Co., Ltd's system). Be blown into after end, be warming up to 100 DEG C, at this temperature, carry out reaction in 8 hours.
Reaction finishes rear use HPLC reactant liquor is carried out to quantitative analysis, result is, has generated 0.172mol β-mercaptopropionic acid sodium salt, 0.013mol thio-2 acid sodium salt and 0.0006mol dithio dipropyl acid sodium-salt as accessory substance.
Similarly neutralize with embodiment 1, extraction, distillation procedure, the β-mercaptopropionic acid (reaction 2) that to obtain 17.5g (0.165mol) be 99.9% as the purity of main distillate fraction. The acrylic acid (14.4g+12.2g) using in reaction with respect to first and bottoms the 1st recirculation, the yield of β-mercaptopropionic acid is 89.2%.
In addition, obtain (β-mercaptopropionic acid 15.3wt% (0.004mol), thio-2 acid 79.3wt% (0.013mol), the dithiodipropionic acid 4.4wt% (0.0006mol)) of 2.9g as pressure bottoms (bottoms (B)).
Be shown in table 1 for composition of the product of the raw material of the reaction in embodiment 5, gained etc.
(embodiment 6)
Similarly react (reaction 1) with embodiment 1. And, using the bottoms (A) after the distillation of gained in reaction 1, change as shown in table 2, for the amount of the raw material of reaction etc., in addition, is reacted (reacting 2) under condition similarly to Example 4. Similarly, gained bottoms in reaction before using, change as shown in table 2, for the amount of the raw material etc. of reaction, in addition, is carried out 4 secondary responses (reacting 3～6) under condition similarly to Example 4.
So, by the bottoms of gained are used for to ensuing reaction, carry out 5 recirculation. As a result, with respect to the acrylic acid that enforcement (reacts 1) for the first time and 1 time～5 times recirculation (reaction 2～6) is used, be 94.4% as the yield of the β-mercaptopropionic acid (purity is 99.9%) that distills main distillate fraction gained.
Be shown in table 2 for composition of the product of the raw material of the reaction in embodiment 6, gained etc.
(comparative example 1)
Preparation has agitating device, thermometer, cooling tube, dropping funel, is blown into 5 mouthfuls of flasks of pipe, pack into after 21.0g (0.51mol) 97% NaOH and 41.6g water, pack 29.6g (0.37mol) 70% sodium bisuflide (with the pure medicine system of light) into, stir until become even.
In oil bath, heat flask, interior temperature is remained on to 45～50 DEG C on one side, dripped 14.4g (0.20mol) acrylic acid on one side by dropping funel through approximately 0.5 hour. After dropping finishes, be warming up to 100 DEG C, at this temperature, carry out reaction in 8 hours.
Reaction finishes rear use HPLC to be analyzed reaction mass, and the yield of result β-mercaptopropionic acid sodium salt is 87.3mol%, generates 12.0mol% thio-2 acid sodium salt and 0.7mol% dithio dipropyl acid sodium-salt as accessory substance.
On one side, to bubbling nitrogen in reaction system, dripped 129.5g (0.462mol) 35% aqueous sulfuric acid, neutralization reaction liquid on one side through 2.5 hours. At this moment the hydrogen sulfide producing is expelled to outside system by condenser top. In addition, the reaction mass composition after neutralization is that the yield of β-mercaptopropionic acid is 79.3mol%, is 12.0mol% as the thio-2 acid of accessory substance, and dithiodipropionic acid increases to 8.7mol%.
After degassed end, carry out the post processing same with embodiment 1, obtain the β-mercaptopropionic acid that 16.2g (0.152mol) is 99.9% as the purity of main distillate fraction. Be 76.1% with respect to the acrylic acid yield packing into.
(comparative example 2)
Preparation has agitating device, thermometer, cooling tube, dropping funel, is blown into 5 mouthfuls of flasks of pipe, packs into after 20.6g (0.50mol) 97% NaOH and 43.3g water, stirs until become even.
In oil bath, heat flask, interior temperature is remained on to 45～50 DEG C on one side, dripped 14.4g (0.20mol) acrylic acid on one side by dropping funel through approximately 0.5 hour.
After dropping finishes, at the same temperature, through 88 points of clockwise reactant liquors, be blown into 12.6g (0.37mol) hydrogen sulfide gas via flowmeter from liquefaction hydrogen sulfide bottle (Sumitomo Seika Co., Ltd's system). Be blown into after end, be warming up to 100 DEG C, at this temperature, carry out reaction in 8 hours.
Reaction finishes rear use HPLC reaction mass is carried out to quantitative analysis, result is, has generated 49.3mol% β-mercaptopropionic acid sodium salt, 48.8mol% thio-2 acid sodium salt and 1.3mol% dithio dipropyl acid sodium-salt as accessory substance.
Embodiment 1～4, comparative example 1～2 the results are summarized in table 3.
The application requires taking No. 2011-253453, the Japanese publication Patent of filing an application on November 21st, 2011 as basic priority, by its disclosed full content introducing the application.
Claims (8)
1. β-mercaptan carboxylic acid's that following general formula (3) represents manufacture method, is characterized in that,Comprise following operation:
Under 0.09～0.13MPa, the alkali metal hydrogen oxidation that hydrogen sulfide, formula XOH are representedThe unsaturated carboxylic acid reaction that thing and following general formula (1) represent, obtains comprising following general formula (2)The operation of the reactant liquor of the compound representing, and
Neutralize the operation of the reactant liquor of gained in aforementioned operation with acid,
Wherein, X represents Na, K, and the amount of described alkali metal hydroxide is described unsaturatedThe more than 1.5 times of the total molal quantity of carboxylic acid and described hydrogen sulfide,
In formula (1), R1、R2Represent respectively the alkyl of hydrogen or C1～C4, can be also identicalCan be different,
In formula (2), R1、R2Identical with the implication in formula (1), X and formula XOH representAlkali metal hydroxide in implication identical,
In formula (3), R1、R2Identical with the implication in formula (1).
2. β-mercaptan carboxylic acid's as claimed in claim 1 manufacture method, is characterized in that,The described operation that obtains reactant liquor is carried out under sulphur exists.
3. β-mercaptan carboxylic acid's as claimed in claim 1 or 2 manufacture method, its featureBe, comprise and use metallic reducing by β-mercaptan carboxylic acid by the described operation of sour neutralization reaction liquidThe operation of the two sulfo-dicarboxylic acids that generate.
4. β-mercaptan carboxylic acid's as claimed in claim 1 or 2 manufacture method, its featureBe, with respect to the total molal quantity of described unsaturated carboxylic acid and described hydrogen sulfide, described alkaliMore than the amount of metal hydroxides is 1.5 times, below 5 times.
5. β-mercaptan carboxylic acid's as claimed in claim 1 or 2 manufacture method, its featureBe, with respect to described unsaturated carboxylic acid, the amount of described hydrogen sulfide is 1.0～9.0 equivalents.
6. β-mercaptan carboxylic acid's as claimed in claim 1 or 2 manufacture method, its featureBe, in the described operation that obtains reactant liquor, reaction temperature is 50～140 DEG C.
7. β-mercaptan carboxylic acid's as claimed in claim 2 manufacture method, is characterized in that,In the described operation that obtains reactant liquor, the addition of sulphur with respect to unsaturated carboxylic acid be 0.1～5 % by mole.
8. β-mercaptan carboxylic acid's as claimed in claim 3 manufacture method, is characterized in that,Described metal is zinc, iron, tin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011253453 | 2011-11-21 | ||
| JP2011-253453 | 2011-11-21 | ||
| PCT/JP2012/007451 WO2013076968A1 (en) | 2011-11-21 | 2012-11-20 | METHOD FOR PRODUCING β-MERCAPTOCARBOXYLIC ACID |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103946210A CN103946210A (en) | 2014-07-23 |
| CN103946210B true CN103946210B (en) | 2016-05-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201280057346.4A Active CN103946210B (en) | 2011-11-21 | 2012-11-20 | β-mercaptan carboxylic acid's manufacture method |
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| Country | Link |
|---|---|
| US (1) | US9206119B2 (en) |
| EP (1) | EP2784064B1 (en) |
| JP (1) | JP5636510B2 (en) |
| KR (1) | KR101584469B1 (en) |
| CN (1) | CN103946210B (en) |
| WO (1) | WO2013076968A1 (en) |
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|---|---|---|---|---|
| US3948816A (en) * | 1971-12-02 | 1976-04-06 | Givaudan Corporation | Mercapto carboxylic acid esters |
| US6689907B1 (en) * | 1995-12-11 | 2004-02-10 | Atofina | Process for the manufacture of mercaptocarboxylic acids from unsaturated carboxylic acids |
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|---|---|---|---|---|
| CH545775A (en) | 1970-12-11 | 1974-02-15 | ||
| JPS5934181B2 (en) | 1975-09-19 | 1984-08-21 | ア−ガス・ケミカル・コ−ポレ−ション | Method for producing mercaptopropionate and polythiodipropionate |
| ES461566A1 (en) | 1976-09-03 | 1978-06-01 | Phillips Petroleum Co | Poly(oxyalkylene)-polyester-poly(sulphide)-polythiols and a process for the preparation thereof |
| JPS5929655A (en) | 1982-08-11 | 1984-02-16 | Nitto Chem Ind Co Ltd | Preparation of beta-mercaptopropionic acid |
| JPS5929633A (en) | 1982-08-12 | 1984-02-16 | Kuraray Co Ltd | Method for recovering acetic acid from aqueous solution of acetate |
| JPS61254555A (en) | 1985-05-01 | 1986-11-12 | Toyo Kasei Kogyo Kk | Production of ester of 3-mercapto-propionic acid |
| JPH02121962A (en) | 1988-10-28 | 1990-05-09 | Daicel Chem Ind Ltd | Production of mercaptocarboxylic acid |
| JP2709650B2 (en) | 1990-04-24 | 1998-02-04 | 富岡化学株式会社 | Production method of β-mercaptopropionic acid |
| US5157147A (en) | 1990-11-05 | 1992-10-20 | Witco Corporation | Method for preparing mercaptopropionic acid esters |
| US5256818A (en) | 1990-11-19 | 1993-10-26 | Tetsuzo Tomioka | Method for making β-mercaptopropionic acid |
| JP2857013B2 (en) * | 1993-04-19 | 1999-02-10 | 株式会社日本触媒 | Method for producing sulfur compound |
| JP2857012B2 (en) * | 1993-04-19 | 1999-02-10 | 株式会社日本触媒 | Method for producing sulfur compound |
| JPH07228568A (en) * | 1993-12-22 | 1995-08-29 | Nippon Shokubai Co Ltd | Production of sulfur compound |
| JPH09249639A (en) | 1996-03-11 | 1997-09-22 | Nippon Shokubai Co Ltd | Production of thiol compound |
| JPH1095760A (en) | 1996-09-19 | 1998-04-14 | Nitto Chem Ind Co Ltd | Production of cyanoacetic ester |
| JP2001187778A (en) * | 1999-12-28 | 2001-07-10 | Mitsubishi Rayon Co Ltd | METHOD FOR PRODUCING beta-MERCAPTOPROPIONIC ACID |
| JP2010095745A (en) | 2008-10-15 | 2010-04-30 | Sumitomo Electric Ind Ltd | Film-forming method and film-forming apparatus |
| WO2010095745A1 (en) | 2009-02-23 | 2010-08-26 | 昭和電工株式会社 | 3-mercaptocarboxylic acid manufacturing method |
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2012
- 2012-11-20 US US14/359,407 patent/US9206119B2/en active Active
- 2012-11-20 EP EP12852300.8A patent/EP2784064B1/en active Active
- 2012-11-20 CN CN201280057346.4A patent/CN103946210B/en active Active
- 2012-11-20 JP JP2013545792A patent/JP5636510B2/en active Active
- 2012-11-20 WO PCT/JP2012/007451 patent/WO2013076968A1/en active Application Filing
- 2012-11-20 KR KR1020147014322A patent/KR101584469B1/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3948816A (en) * | 1971-12-02 | 1976-04-06 | Givaudan Corporation | Mercapto carboxylic acid esters |
| US6689907B1 (en) * | 1995-12-11 | 2004-02-10 | Atofina | Process for the manufacture of mercaptocarboxylic acids from unsaturated carboxylic acids |
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| Publication number | Publication date |
|---|---|
| CN103946210A (en) | 2014-07-23 |
| EP2784064A1 (en) | 2014-10-01 |
| KR20140084309A (en) | 2014-07-04 |
| US20140288329A1 (en) | 2014-09-25 |
| EP2784064B1 (en) | 2017-01-04 |
| WO2013076968A1 (en) | 2013-05-30 |
| EP2784064A4 (en) | 2015-07-22 |
| JPWO2013076968A1 (en) | 2015-04-27 |
| JP5636510B2 (en) | 2014-12-03 |
| US9206119B2 (en) | 2015-12-08 |
| KR101584469B1 (en) | 2016-01-19 |
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